Citation: Fu Wenwen, Li Yan, Liang Changhai. Dehydrogenation Mechanism of Ethanol on Co(111) Surface: A First-principles Study[J]. Acta Chimica Sinica, ;2019, 77(6): 559-568. doi: 10.6023/A19010020 shu

Dehydrogenation Mechanism of Ethanol on Co(111) Surface: A First-principles Study

Fu Wenwen ^a ,
Li Yan ^b,, ,
Liang Changhai ^a,,

a.
State Key Laboratory of Fine Chemicals, School of Petroleum and Chemical Engineering, Dalian University of Technology, Panjin 124221
b.
School of Chemical Engineering, University of Science and Technology Liaoning, Anshan 114051

Corresponding author: Li Yan, snow2007liyan@163.com Liang Changhai, changhai@dlut.edu.cn
Received Date: 10 January 2019
Available Online: 12 June 2019
Fund Project: the National Natural Science Foundation of China 21573031Project supported by the National Natural Science Foundation of China (No. 21573031)

Figures(11)

The detailed reaction mechanism of ethanol dehydrogenation on Co(111) surface was studied using the density functional theory (DFT) and slab periodic model. The structures and energies of the species involved in the reaction adsorbed on different adsorption sites (top, fcc, hcp and bridge sites) of the surface were calculated and compared. The calculated results show that ethanol adsorbs weakly on the Co(111) surface. CH₃CH₂O, CH and C prefer hcp sites with adsorption energies of -2.72, -6.85, and -6.92 eV, respectively. CH₃CHO adsorbs weakly at the bridge-η¹(O)-η¹(C^α) site with adsorption energy of -0.47 eV. CH₃CO and CH₂ adsorb stably on Co(111) surface through their unsaturated C atoms with binding energies of -2.31 and -3.90 eV, respectively. CH₃ and CH₄ prefer to locate at top sites through the C atom with adsorption energies of -1.95 and -0.12 eV, respectively. CO and H are bind stably at fcc sites with binding energies of -1.62 and -2.77 eV, respectively. Due to the complexity of the decomposition of ethanol, the scissions of O-H, C-H, C-O and C-C bonds of CH₃CH₂OH were examined. The results show that ethanol decomposition on Co(111) surface starts with the scission of the O-H bond, and the dehydrogenation reaction of ethanol on Co(111) surface can be described as three reaction pathways:Path Ⅰ is the gradual dehydrogenation of CH₃CH₂OH via intermediate CH₃CHO, which ultimately produces CH₄ and CO; Path Ⅱ is the reaction of CH₃CH₂O and CH₃CHO which were generated by dehydrogenation of ethanol, to form CH₄ and CO₂ via CH₃COOH intermediate; Path Ⅲ is the process of CH₃CH₂O reacts with CH₃CO to generate CH₃COOC₂H₅. On the basis of our computational results, Path Ⅰ (CH₃CH₂OH→CH₃CH₂O→CH₃CHO→CH₃CO→CH₃+CO→CH₂→CH→CH₄+CO+C+H) is more favorable than Paths Ⅱ and Ⅲ and the dehydrogenation of CH₃CH₂O to CH₃CHO is the rate-determining step with a reaction energy barrier of 1.61 eV.
- first principle,
- ethanol,
- Co(111) surface,
- dehydrogenation,
- adsorption
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